Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
  • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
  • C07D493/10—Spiro-condensed systems
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
  • B41M5/132—Chemical colour-forming components; Additives or binders therefor
  • B41M5/136—Organic colour formers, e.g. leuco dyes
  • B41M5/15—Spiro-pyrans
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
  • Y10S8/916—Natural fiber dyeing
  • Y10S8/919—Paper

Definitions

• alkoxy and carbalkoxy radicals with which the aromatic nucleus A may be sub- 10 stituted are carbomethoxy, carboethoxy, methoxy and ethoxy in the position 6 when A is a benzene nucleus and in position 10' when A is a naphthalene nucleus.
• Preferred sites of substitution of the nucleus are position 6 in the case of benzene and position 10 in the case of naphthalene, the naphthalene nucleus itself being preferably in the position 2,1-b on the pyrylium in which nucleus.
• A denotes a benzene or naphthalene nucleus option- Particularly preferred values of R are methyl and ally substituted by chlorine, bromine, or alkoxy or isopropyl. lcarbalkoxy radlcals Preferred values of R are methyl, ethyl, propyl, tdenotes alkyl of from 1 to 8 Carbon atoms butyl, phenyl and also a trimethylene bridging group R denotes hydrogen or alkyl or aryl of from I 8 connecting the positions 3 and 3 of the two pyrylium caribon atoms, or R and R together form a ring, nuclei, and hydrogen an a 4 R and R denote C alkyl optionally substituted by Preferred values of R R are methyl ethyl pyl and B-cyanoethyl, R being preferably the same as cyano. R4 The spirodipyrans of formula I are colorless or slightly colored compounds. When dissolved in
• the condensation is conveniently carried out in organic solvents such as alcohols, carboxylic acids, carboxylic anhydrides, carboxamides, hydrocarbons and acetonitrile and in the presence or absence of acidic or basic condensating agents such as zinc chloride, phosphoric acid, toluenesulfonic acid, boric acid, pyridine, piperidine,triethylamine and ammonium acetate in the amountsand under the conditions normally used in condensation reactions of this kind.
• organic solvents such as alcohols, carboxylic acids, carboxylic anhydrides, carboxamides, hydrocarbons and acetonitrile
• acidic or basic condensating agents such as zinc chloride, phosphoric acid, toluenesulfonic acid, boric acid, pyridine, piperidine,triethylamine and ammonium acetate in the amountsand under the conditions normally used in condensation reactions of this kind.
• the ring closure to the pyran may take place either at the same time as or subsequently to the condensation in the same or a separate stage, optionally in the presence of bases such as alkalis, sodium carbonate, sodium acetate, ammonia, aliphatic amines and pyridine, in known manner.
• bases such as alkalis, sodium carbonate, sodium acetate, ammonia, aliphatic amines and pyridine, in known manner.
• bases such as alkalis, sodium carbonate, sodium acetate, ammonia, aliphatic amines and pyridine, in known manner.
• the spirodipyran compounds which precipitate from the solution in the form of crystals may then be used in known manner as dye precursors in copying processes.
• a particularly advantageous process consists in dissolving the dye precursors in a non-volatile or only slightly volatile solvent such as chloroparaffin or trichlorodiphenyl, or in a normal solvent such as toluene, and enclosing the solution in microcapsules and coating the surface of paper with said microcapsules.
• these precursors When pressed against an acid reacting layer by a writing operation, these precursors produce blue characters]
• the compounds of the invention are distinguished by their very high color strength and .by the excellent photocopies which can be made of the characters produced with said compounds.
• EXAMPLE 1 35.7 parts of 2,3-dimethylbenzopyrylium tetrachloroferrate and l 9.3 parts of diethylaminosalicylaldehyde are heated under reflux in 200 parts of ethanol for 2 hours. On completion of the condensation, the dye is isolated, dissolved in 200 parts of acetone and mixed with 80 parts of ammonia solution and 250 parts of water. The reaction mixture is extracted with 700 parts of benzene. The benzene phase is separated, purified with animal charcoal, dried over sodium sulfate and concentrated to a volume of approx. 200 parts.
• EXAMPLE 2 81.4 parts of .2,3-dimethylnaphthopyrylium tetrachloroferrate and 36.6 parts of diethylaminosalicylaldehyde are heated under reflux in 200 parts of ethanol for 1 hour. After the elimination of acid from the dye using ammonia as described in Example l, there are obtained 52 parts of the colorless compound 3 -methyl-7-diethylaminospiro-( 2 H l-benzopyran-2,2'-[21-l]-naphto[2.l-b]pyran), m.p. 18l-l82C.
• EXAMPLE 3 15 parts of 2,3-dimethyl-10-carbomethoxynaphthopyrylium tetrachloroferrate and 6.3 parts of die thylaminosalicylaldehyde are heated under reflux in parts of ethanol for 5 hours.
• Papers coated with this compound in microcapsules give a blue coloration when pressed against an acid reacting layer by a writing operation.
• EXAMPLE 4 20 parts of 2-methyl-3-isopropylbenzopyrylium tetrachloroferrate and 1 4.5 parts of diethylaminosalicylaldehyde are heated under reflux in parts of ethanol for 40 minutes. The dye thus formed is converted, as in Example 1, to the colorless compound 3'-isopropyl-7-diethylamino-2,2'- spirodi[2H-l-benzopyran], m.p. 9698C.
• This compound gives a blue coloration when contacted with an acid reacting substance.
• the dye precursor is eminently suitable for the manufacture of copying papers on account of its high tinctorial strength.
• EXAMPLE 5 16.7 parts of 2,3-tetramethylene-naphthopyrylium perchlorate and 9.6 parts of diethylaminosalicylaldehyde are heated under reflux in 100 parts of ethanol for 25 minutes. The dye is isolated and stirred in 30 parts of 25% ammonia solution and 300 parts of benzene until the color disappears completely. The benzene phase is separated, purified with animal charcoal, dried over sodium sulfate and concentrated.
• Example 6 A solution of this compound in chlorinated diphenyl in microcapsules gives a blue coloration as in Example EXAMPLE 7
• Example 6 is repeated except that in place of 2,3-tetramethylenenaphthopyrylium perchlorate 2,3- tetramethylene- -carbomethoxynaphthopyrylium 1 perchlorate is reacted with diethylaminosalicylaldehyde. There is obtained a compound which gives bluish violet colorations when contacted with acids.
• EXAMPLE 8 35.7 parts of 2,3-dimethylbenzopyrylium tetrachloroferrate and l 6.5 parts of dimethylaminosalicylaldehyde are heated under reflux in I 100 parts of alcohol for 2 hours.
• the dye thus formed is converted, as described in Example 1, to the colorless compound 3-methyl-7- dimethylamino-2,2-spirodi[2 H-l-benzopyran], m.p. l47l48C.
• EXAMPLE 9 40.7 parts of 2,3-dimethylnaphthopyrylium tetrachlorofe rrate and 16.5 parts of dimethylaminosalicylaldehyde are heated under reflux in 100 parts of alcohol for 2 hours.
• the dye is treated with ammonia as described in Example l to give 23 parts of the colorless compound 3- methyl-7-dimethylaminospiro( 2 H- l -benzopyran-2,2
• This compound gives a blue coloration when contacted with acid reacting substances.
• A is a benzene or naphthalene nucleus optionally substituted by one chlorine atom, one bromine atom, or one carbomethoxy or one carbethoxy group,
• R is methyl or isopropyl
• R is hydrogen, or R and R together form a trimethylene radical
• R and R are methyl, ethyl or propyl.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Color Printing (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

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• 1973
  • 1973-06-26 DD DD171960A patent/DD109871A5/xx unknown
  • 1973-06-27 GB GB3062373A patent/GB1426396A/en not_active Expired
  • 1973-06-28 FR FR7323672A patent/FR2190816B1/fr not_active Expired
  • 1973-06-28 IT IT51108/73A patent/IT988290B/it active
  • 1973-06-28 US US374353A patent/US3899514A/en not_active Expired - Lifetime
  • 1973-06-28 CH CH945673A patent/CH578002A5/xx not_active IP Right Cessation
  • 1973-06-28 CA CA175,148A patent/CA998681A/en not_active Expired
  • 1973-06-29 BE BE132934A patent/BE801694A/xx not_active IP Right Cessation
  • 1973-06-30 ES ES416481A patent/ES416481A1/es not_active Expired
  • 1973-07-02 JP JP7377373A patent/JPS5544782B2/ja not_active Expired

Patent Citations (1)

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